Dyeing process



Patented 26, 1 930 's- UNITED srATEs PATENT arms auous'rn nscnrcn can: munwoaus, or rams, M01! prams rnocnss Io Drawlng.- Application fled November 20, 1888, Serial No. 875,880; and infiermany November 25, 1885 This invention relates to a (I sing process thatjnay be applied to hot vegetable and animal fibres, whether in the thread form or woven, to feathers, furs, ammal and vegetable hairs, leathers, artificial silks,

woods, gelatines and the like.

In the process-a bath may be immediately prepared when required by:

(a) either dissolving mixtures prevlous- 1y repared in the industry, in accordance wit the instructions hereinafter given.

(b) or by applying and varying the formulae given as examples, to obtain coloring baths acting immediately with hot treatment, or more slowly and within about 24 hours with cold treatment.

(c) or by transforming into colorless chromogenes already fixed on the fibre.

The principles underlying the process are as follows:

I. All substances having the properties of phenol, their salts and derivatives and in particular the soluble salicylates, salicylic acid dissolved in water with or without an adjuvant capable of increasing its solubility, yield, in a more or less acid medium, powerful colorants with the soluble nitrites or the vapors of nitrous acid and in the presence of metallic oxides or salts.

The same holds good for primary amines of the aromatic series capable of being converted into phenolic bodies under the action of nitrous acid by the hot process.

The bringing of freshly formed nitrous acid into contact with the material to be dyed will, generally, be effected by adding a nitrite of an alkali metal to the dye-bath and by the simultaneous'or subsequent action of an acid.

In certain cases, however, nitrous acid conveyed by air, gas or steam may be utilized.

II. Substances functioning as an acid,

Certain mixtures which at first would seem to be useless manifest ano less degree of activity, the decomposition of the nitritesbeing sufliciently capricious and sometimes" independent of the reaction of the medium. It is thus that the mixture salicylate with iron perchloride and a nitrite and Seignette salt produces the same green as if an acid were present. By Seignette salt we mean double tartrate of potassium and sodium, whose generally adopted formula is G H NaK+ 411.0,

and which is used for pharmaceutical and tinctorial purposes.

III. Salicylic acid or the soluble salicylates in the presence of a metallic salt, attach themselves to the animal fibres and fix the salt there, whence, after washing, a fabric so prepared will acquire color, with or without applied heat, in a colorless bath containing freshly formed nitrous acid, the operation recalling that of diazotization. This fixing takes place even on cotton or on artificial silk under heat and could be retained as a means of producing weak colors.

Thus if a cotton fabric is immersed in sodium salicylate a copper chloride and nitrous acid heat: a rose is obtained after washing in water to which ammoniacal water has been added or which has been pyridinized.

IV. The intensity of the color varies with ghehpercentage of phenolic substance in the Example: 100 c. 0. solution of sodium salicylate at 1% strength gms. nickel chloride 0.50 gms. sodium nitrite 20 drops acetic acid heat: a salmon rose is obtained.

With the same throughout, except 0.40 gms. salicylate added: a redder tint is obtained.

The same in every respect, except that an additional 2 gms. of salicylate are employed, a deep red is obtained.

V. The shades vary not only with the metallic base of the salt or the oxide (yellows with the ferrous salts, greens with ferric salts, reds with nickel or copper salts) but also with the proportions of salt or of oxide contained by the bath.

Examples: 100 c. c. aqueous solution ofsodium salicylate at 5% 0.50 s. cobalt chloride 0.25 gms. sodium nitrite 20 dro s of crystallizable acetic acid, produce a ten ency to black on wool or silk sam Ice.

The same, except 0.10 gms. of coba t chloride instead of 0.50 gms.: deep brown (tte' de negre) is produced.

The same, except that only 0.01 gms. cobalt chloride are used instead of 5 gms. gives a more obvious tendency to red.

Two metallic salts or metallic oxides in conjunction, will lead to modifications which vary with their total weight and their respective percentages.

A double salt will yield the effects of its constituents.

VI. The metal alone, that is to say which is not oxidized and not used in the form of a salt, is capable of developing the color obtained with one of its oxides or salts; the metal can be used in a pure state in the form of plates, threads or owders, so as to draw therefrom several di erent practical results; by applying the metal at selected places on a fabric, the latter will develop the special color of the metal at the place where it will be in contact with the said fabric, thereby allowing to obtain polychromic effects in simultaneously using several metals.

But if a color produced by a determined metal has been develo d on the fibre, it will be very easy to substitute for this color the color of another metal if the latter removes the other metal from its combinations according to the laws of Richter about the electrochemical classification of metals.

Example: If, upon a fabric dyed by sodium salicylate and copper sulphate and before washing a disc of iron is laid, the latter will ra idly produce a green color on the original red ground.

The employment of thickening agents will facilitate this kind of multiple-dyeing and will furnish means of more or less replacing stamped impression. I

Example: If a mixture consisting of sufiicient quantities of thickening agents and a solution of salicylate is divided and to one part is added a ferric salt, to another a copper salt and to a third cobalt salt, etc. and a wool or silk fabric is touched at different places with each of them, the latter will, after a few minutes, be in a condition for washing and if it is then introduced into an atmosphere containing nitrous acid or into a bath, even cold, containing freshly formed nitrous acid, the colors corresponding to the metallic salts employed will make their appearance.

VII. Light, having, in general, a reduc/ ing effect on the various metallic salts in' their highest valency, (ferricyanide, ferric salts, manganese, mercury, cobalt, uranium, bichromate salt, etc.) it is obvious that the insolated parts on a dr fabric will not assume the same color as t e rest.

Example: Regions which, by being insolated, have become ferrous, will yield yellows while the protected parts, which have remained ferric, will, on development, yield greens.

The percentages of sodium nitrite may be those of diazotization (15 to gms. to 20 litres of bath) but no harm is done b an excess and an amount of 50 gms. to 20 litres of bath will often be conducive to the beauty of the colors. The examples cited make use of this figure.

Theoretically, the equation, sodium nitrite +acid=nitrous acid and sodium salt of the acid, is a sufiicient guide in determining the weight of the acid.

In practice, two typical formulae have yielded excellent results:

Water 20 litres Sodium salicylate 100 grams. Sodium nitrite 15 to 50 grams.

Acetic acid of 10 Baum or an equivalent acid to grams.

The latter formula shows that the acids or I acid salts are only necessary if salicylate is made use of to start with, but it is more economical to employ the salicylic acid itself, either in the amorphous or crystalline form.

According to the particular tint desired, the metallic salt added must be varied: thus, the following examples may be given:

1. The simplest example is that of the yellows furnished by the bath, by salicylic acid nitrite and particularly by aniline salicylic acid nitrite, thus demonstrating the possibilities within reach by mixing different color producers.

2. Ferric salts: 2 gms. to 20 litres of a bath containin ordinary commercial solid iron perchlori e Will yield, in conjunction with salicylate, a color yellow on wool by'heating below the boiling point.

(a) With 10 gms. of perchloride there is obtained on wool and silk a deep green, which begins to appear at about 50 C. when the bath is still red and does not begin to become green till the temperature is about or (b) With 20 gms. perchloride, a sombre green is obtained, more especially on wool.

(c) With 40 gms. a brighter green is produced.

Ferrous salts yield yellows.

Without heat, the same colors will make their ap earance in aboutji hours. Thei may be 0 tained also from the simple combination (salicylate iron perchloride,'Tgr.

"in the previous case. '7

all

4. Commercial chromium chloride; 2 gms. per 20 litres yields a reddish yellow on wool and silk.

20 gms. give copper browns.

100 gms. give browns.

Thus it is evident that the quantity of Inctallic salt or oxide used exercises considerable modifying influence on the resulting colors.

As a general rule, with an average percentage of'50 gms. per 20 litres bath, various reds will be produced by the salts of copper, nickel mercury, green uranium oxide, the sodium or potassium uranate, arsenious acid, lead eroxide, ammonium molybdate, and the 'ke.

The greens are the production of the ferric salts, etc.

Various yellows, of greater or less depth, will be produced by potassium 'ferricyanide, the bioxide and the salts of molybdenum or bismuth in an acetic or other acid solution by antimonic acid, by the tungstates, by the oxide and salts of mm, by the aluminium salts,

by manganese bioxide-barium peroxide, ar-

senic acid, stannic salts, manganesechloride, potassium permanganate, by yellow chromlate and by phosphomolybdic acid and the li e.

Every'metallic salt may be made use of whatever be the reacting acid (sulphates, chlorides, chromates, acetates, etc.).

If they are insoluble, the metallic oxide and sulphides should be enclosed in bags made of a sufficiently close fabric. The hydrated oxides may be produced in the bath.

Example: sodium salicylate copper sulphate potash enough acetic acid to redissolve the precipitate nitrite, withv suitable heat, yields striking reds.

A mixture of two metallic salts acting in presence of a salicylate or of salicylic acid and freshly formed nitrous acid will modify the shades considerably.

Example: 20 litres salicylated water 20 gms. potassium ferricyanide 15 gms. corrosive sublimate 25 gms. sodium nitrite -l 200 gms. acetic acid: a green will be obtained at boiling point, whereas the ferricyanide alone would have produced yellows and the sublimate reddish hue.

Another example: The mixture (salicylate, copper chloride and sublimate in equal proportions) nitrite acetic acid produces yellows of a more or less a purple reds.

: The sodium salicylate and the salicylic acid may be replaced by substitutes.

Potassium salicylate leads, in general, t0 the same results as sodium salicylate, however, it does not redden by transition in the production of green from ferric anide with sublimate. Ammonium green. I a

The magnesium salicylates'and/or lithium salicylate do-not even require nitrite in order to yield a clear .green with the ferricyanide,

sublimate and acetic acid.

These transitory tints are, moreover, due to the reduction of the ferricyanide.

Salicylic aldehyde would give the same results as the acid, but enfeebled owingto the reduced solubility. 1

Sulphosalfcylic acid, acetylsalicylic acid, antipyrin salicylate and salicylamide give weaker results. None the less the acids of this class, it will be understood, may be substituted for the ordinary acids in the bath (salicylate metallic salt nitrite).

Benzoic, cinnamic, paraoxybenzoic and orthoamidobenzoic acids are, for this purpose, inferior to salicylic acid.

Another method of procedure consists in making use as already indicated, of thickening agents charged with varying mixtures (sodium salicylate a metallic salt) :the color is then developed in an; aqueous or gaseous bath of nitrous acid.

Here is a method of imprinting wherein use may be made of the ordinary equipment (board, perrotine, drawing-pen) with the condition, however, that account is taken of incompatible metallic associations: the employment, for example, of iron tools with copper salts, of copper tools with salts of mercury, etc., must be avoided. Further, woods rich intannin would acquire a counter (or negative) imprint with ferric salts, the molybdat es, etc.

Other methods are also. available, such as the following Immersion, for a longer or shorter time, of the fabric in an incomplete bath (salicylate metallic salt nitrite) then, without washing, the color may be made to appear at spots which have been touched by an acid embodied in a thickening agent or by means of a device feeding a fluid charged with acid vapors.

Finally, if an animal fibre is impregnated with an acid which it retains even after washing the acidification of the bath (salicylate metallic salt nitrite) is not necessary.

Phenol and Dem'oatioes.-The reactions of these substances capable of use in industry are indicated by those for salicylic acid.

The metallic salts, acids and nitrites will be employed in the same proportion as indicated in the case of the phenol acids. The proportion of phenol or sodium phenate salicy ate passes' through a scale of blues before arriving at.

present in the bath being from 80 to 100 ms. per lit-res of water, the general ormula already given will be applicable.

Example J.Phenol 300 c; c. acetic solution of mercury oxide (the latter in roportions varying with the metallic sa ts) nitrite, yields a special and very pleasing red.

Emampla ?2.Sodium phenate (or phenol asufliciency ofalkali to saturate) potassium ferricyanide sublimate acetic acid nitrite, yields greens.

Ewample 3.-Phenol copper sulphate potash or soda in suflicient quantity to cause precipitation a sufficiency of acetic acid to redissolve the precipitate and acidulate nitrite, produces reds.

The different metallic salts or oxides may be employed in varying proportions, under the same conditions as in the case of the phe- 20 uol acids; the practical operations are the same.

Resorcin and derivaz rca-Resorcin is capable of being employed as a dyeing agent lilie the phenol substances already dealt with; its

33 derivatives, such as the diamido or dinitroresorcin are still more so.

It suffices to apply the methods which are practical in the preceding case, that is, to cause the nitrous acid to react in the presence at of metallic salts.

The proportion of resorcin will be from 50 to 100 gms. per 20 litres bath. As being dearer, though much more sensitive, the derivatives may be made use of in such quanti- 35 ties as their price allows. The different developers are used in the proportions indicated in the foregoing cases.

Example: .resorcine, salt of copper, nitrite and acid give in the hot as in the cold state m a yellowish'red.

If the salt of copper is replaced by a salt of mercury, a yellow will be obtained, and'if replaced by a ferric salt, a fine green which can be brought as far as black, etc., Will be :7, obtained.

In the same conditions, it is possible to use -instead of resorcine, dinitroresorcine or di-- amidoresorcine. The addition of urea allows of shading the colors.

If cobalt sulphate be substituted for copper sulphate, diamido-resorcin yields brownish rods on silk, cotton and wool while the dinitro-rrsorcin yields various shades. By adding urea in varying proportions to the bath,

.13 the shades may also be modified.

A striking example may be given. A cotton tissue mordanted with resorcin at 5% strength, then washed and immersed in a nitrous bath in presence of a cobalt salt acne quires an interesting saffron color. It should be noted that resorcin attached to vegetable fibres, forms in general, a good mordant for the coloring agents derived from the phenol acids.

or N apht/r0Z.The naphthols fix readily to the fibres and it is possible, after washing, to develop the tints on this mordant by the aid of the appropriate reactions.

or naphthol is sufficiently soluble in acetic acid and advantage must be taken of this property from the fact that the freshly ormed nitrous acid set free from nitrites by the acetic acid, gives rise to a series of chromatic reactions with o: naphthol in the presence of different metallic salts (hydrates redissolved in acetic acid or other organic acids.

Example: 20 litres Water a variable proportion of a metallic salt or oxide of the copper group (especially nickel, cobalt) 20 guns. or naphthol dissolved in soda and added to the bath +a sufficiency of an acid and especially of an acid salt, for example, soluble potassium bitartrate. to redissolve 50 to 100 'gms. sodium nitrite, produces various tints on cotton and all fibres, yields also reds with copper, and kermes browns with nickel and cobalt.

The quantity of the metallic salt of oxide will range from 20 to 100 gms. Brighter reds may be obtained in a similar manner, from the precipitated and redissolved mercury salts or by taking advantage of the solubility of a naphthol and of the red mercury oxide in acetic acid and of the fact that a fabric may be mordanted in this solution if diluted; it will then suffice after washing, to introduce the fabric into a bath of freshly formed nitrous acid or an atmosphere charged with it.

The derivatives of a naphthol may be similarly made use of.

,8 Nap7ztk0Z.All the reactions described in the foregoing paragraphs may be effected with [3 naphthol, when it has been rendered soluble in soda.

The reactions of the metallic salts and oxides in the presence of freshly formed nitrous acid may be employed under the same conditions as for a naphthol, but will lead to different dyeing effects.

Example: [3 naphthol soda in sufficient quantity copper sulphate soluble potassium bitartrate nitrite in proportions similar to those indicated for a naphthol, yields yellows, withheat, on all fabrics.

The same processes may be employed with only this difference that ,8 naphthol, being less soluble than a naphthol in acetic acid, it will be necessary to mordant more thoroughly at first with the alkali and B naphthol and then to transfer the fabric, when washed, to the bath (metallic oxide, hydrated or anhydrous sufficiency of acetic acid to neutralize and acidulate nitrite).

The derivatives of B naphthol (Schaffers salt, salt R, salt G, etc.) may be employed under the same conditions as those of or naphthol (salt N. W., salt R. G., Schoellkopfs salt, etc.)

The following remarks are common to both naphthols.

If, for example, copper and a naphthol have been fixed on cotton by the help of dilute Fehlings liquor, the fabric will acquire a lilac gray tint in the presence of nitrous acid.

The metallic salts or oxides which are not precipitated by the alkalis in the presence of the tartrates, or of glycerine or of sugar may be employed in the same manner; this, there: fore, is a general method of mordanting which may be serviceable in many cases, by making use, in the presence of metallic salts, of phenolic compounds or other substances which are soluble in the alkalis.

Tannrim'.The tannins, considered as polyphenols act in the same way as the phenolated substances which have been previously mentioned; then there is no formation of metallic tannates which would precipitate; on the contrary the methods proposed by the present text tend to avoid every precipitation and to always proceed in a clear bath.

Thus a bath of a salt of molybdene and of tannin in which nitrous acid has been produced, will develop a golden color.

If one replaces molybdene by a salt of zinc, this produces a very fine mahogany color, if replaced by a salt of nickel, a color nearing the red will be obtained.

Amines.The primary amines ofthe aromatic series, their salts and derivates, being transformed when treated in the hot state by the action of nitrous acid into bodies functioning as phenol, it is possible to use these primary amines as phenols in the presence of metallic compounds and nitrous acid for dyeing the fibres according to the present process.

Example: 20 litres water 20 gms. aniline hydrochloride 20 to 100 gms. of a soluble salt of nickel nitrous acid give reddish yellow shades; The addition of ferricyanide to the bath renders the red more accentuated but makes the liquid veryfrothy.

Example: 20 litres water 200 c. 0. aniline 20 acetic acid of 10 B. produces a yellow and thereafter a brownish yellow WhlCh may be utilized besides, without any treatment elther with soda or alcohol, as a coloring agent for all fibres, after filtration. As the salt of diazobenzene is destroyed by heat, if to the filtrate there is added a nickel salt for example, and also nitrites, and acid, a red color is produced.

Example: The-filtrate of the above case, treated with 20 to 40 gms. oxidizing agents (as, for instance, by 24/25ths persulphate 1/25th copper) produces on all fabrics even without heat, very intense rowns approximating to blacks.

The diiierent method above described concerning the salicylates are also available in gms. sodium nitrite 100 c. c.-

fibres comprising subjecting the same to' treatment, at a temperature comprised between the ambient temperature and the boiling point of water, in a-bath which contains a metallic substance other than an alkali metal or alkali-earth-metal, freshlyformed nitrous acid and a phenolic body, all in state of complete solution.

2. Process for dyeing and printing on all fibres comprising subjecting the same to treatment, at a temperature lower than the boiling point in a bath in which have been completely dissolved a metallic substance other than alkali-metal or alkali-earthmetal, freshly formed nitrous acid and a primary amine of the aromatic series, the temperature of the bath being high enough to transform the said primary amine in the presence of nitrous acid into a phenolic body.

In testimony, that we claim the foregoing as our invention, we have signed our names in the presence of two subscribing witnesses.

AUGUSTE ESCAICH.

JEAN PAUL WORMS. 

